{"title":"Two-Dimensional Silver-Isocyanide Frameworks.","authors":"Kaiyue Jiang, Pu Yan, Pengfei Shi, Jichao Zhang, Xinyu Chai, Yunfei Wang, Chenhui Zhu, Chongqing Yang, Chenbao Lu, Yi Liu, Kecheng Cao, Xiaodong Zhuang","doi":"10.1002/anie.202417658","DOIUrl":null,"url":null,"abstract":"<p><p>Metal-organic frameworks (MOFs) have been widely studied due to their versatile applications and easily tunable structures. However, heteroatom-metal coordination dominates the MOFs community, and the rational synthesis of carbon-metal coordination-based MOFs remains a significant challenge. Herein, two-dimensional (2D) MOFs based on silver-carbon linkages are synthesized through the coordination between silver(I) salt and isocyanide-based monomers at ambient condition. The as-synthesized 2D MOFs possess well-defined crystalline structures and a staggered AB stacking mode. Most interestingly, these 2D MOFs, without π-π stacking between layers, exhibit narrow bandgaps down to 1.42 eV. As electrochemical catalysts for converting CO2 to CO, such 2D MOFs demonstrate Faradaic efficiency over 92%. Surprisingly, the CO2 reduction catalyzed by these MOFs indicates favorable adsorption of CO2 and *COOH on the active carbon sites of the isocyanide groups rather than on silver sites. This is attributed to the critical σ donor role of isocyanides and the corresponding ligand-to-metal charge-transfer effect. This work not only paves the way toward a new family of MOFs based on metal-isocyanide coordination but also offers a rare platform for understanding the electrocatalysis processes on strongly polarized carbon species.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1000,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/anie.202417658","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Metal-organic frameworks (MOFs) have been widely studied due to their versatile applications and easily tunable structures. However, heteroatom-metal coordination dominates the MOFs community, and the rational synthesis of carbon-metal coordination-based MOFs remains a significant challenge. Herein, two-dimensional (2D) MOFs based on silver-carbon linkages are synthesized through the coordination between silver(I) salt and isocyanide-based monomers at ambient condition. The as-synthesized 2D MOFs possess well-defined crystalline structures and a staggered AB stacking mode. Most interestingly, these 2D MOFs, without π-π stacking between layers, exhibit narrow bandgaps down to 1.42 eV. As electrochemical catalysts for converting CO2 to CO, such 2D MOFs demonstrate Faradaic efficiency over 92%. Surprisingly, the CO2 reduction catalyzed by these MOFs indicates favorable adsorption of CO2 and *COOH on the active carbon sites of the isocyanide groups rather than on silver sites. This is attributed to the critical σ donor role of isocyanides and the corresponding ligand-to-metal charge-transfer effect. This work not only paves the way toward a new family of MOFs based on metal-isocyanide coordination but also offers a rare platform for understanding the electrocatalysis processes on strongly polarized carbon species.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.